Acyl hydantoin phosphorothioates

ABSTRACT

ACYL HYDANTOIN DERIVATIVES DEFINED BY THE FOLLOWING STRUCTURAL FORMULA:   2,4-DI(O=),1-R1,3-(X-C(-R6)(-R7)-CO-),5-R2,5-R3-IMIDAZOL-   IDINE   WHEREIN R1 IS ONE SELECTED FROM THE GROUP CONSISTING OF C1-C6 LOWER ALKYL, OPTIONALLY SUBSTITUTED BY CHLORINE, BROMINE, C1-C6 ALKOXY AND C1-C6 ALKYLTHIO; C3-C6 ALKENYL, C3-C6 ALKYNYL, C3-C9 CYCLOALKYL, PHENYL OPTIONALLY SUBSTITUTED WITH CHLORINE, BROMINE, TRIFLUOROMETHYL OR NO2, R2 AND R3 CAN BE THE SAME OR DIFFERENT AND EITHER ONE IS SELECTED FROM THE GROUP CONSISTING OF HYDROGEN, C1-C4 ALKYL, C1-C4 CHLOROALKYL, PHENYL OPTIONALLY SUBSTITUTED WITH CHLORINE OR NITRO AND C1-C4 ALKOXY. X IS ONE SELECTED FROM THE GROUP CONSISTING OF CHLORINE, BROMINE, FLUORINE AND A MOIETY DEFINED BY   -S-P(=Y)(-R4)-R5   WHEREIN Y CAN BE EITHER O RO S AND R4 AND R5 CAN BE THE SAME OR DIFFERENT AND SELECTED FROM THE GROUP CONSISTING OF C1-C6 ALKOXY, C1-C6 ALKYL, C1-C6 ALKYLTHIO, PHENYL OPTIONALLY SUBSTITUTED WITH CHLORINE OR BROMINE, PHENOXY OPTIONALLY SUBSTITUTED WITH CHLORINE OR BROMINE; R6 AND R7 CAN BE THE SAME OR DIFFERENT AND CAN BE SELECTED FROM THE GROUP CONSISTING OF HYDROGEN, AND C1-C6 ALKYL. ORGANIC COMPOUNDS REPRESENTED BY THIS STRUCTURE HAVE BEEN FOUND TO HAVE PESTICIDAL, PARTICULARLY INSECTICIDAL, ACTIVITY. COMPOUNDS REPRESENTED BY THE FOLLOWING STRUCTURE:   1-R1,2,4-DI(O=),3-(Q-C(-R6)(-R7)-CO-),5-R2,5-R3-   IMIDAZOLIDINE   HAVE BEEN FOUND TO POSSESS POST-EMERGENCE HERBICIDAL ACTIVITY. IN THIS STRUCTURE, R1, R2, R3, R7 AND R6 ARE DEFINED AS HEREINABOVE, AND Q IS ONE SELECTED FROM THE GROUP CONSISTING OF CHLORINE, BROMINE AND FLUORINE.

United States Patent 3,780,056 ACYL HYDANTOIN PHOSPHOROTHIOATES GophalH. Singhal, 612 Ardsleigh Drive, Westfield, N.J., and Joseph H. Lesser,3901 62nd St., Woodside, NY. N0 Drawing. Original application Apr. 23,1970, Ser. No. 31,405, now abandoned. Divided and this application Dec.17, 1971, Ser. No. 209,385

Int. Cl. C07f 9/06 US. Cl. 260-3095 6 Claims ABSTRACT OF THE DISCLOSUREAcyl hydantoin derivatives defined by the following structural formula:

wherein R is one selected from the group consisting of C -C lower alkyl,optionally substituted by chlorine, bromine, C -C alkoxy and C -Calkylthio; C -C alkenyl, C -C alkynyl, C -C cycloalkyl, phenyl optional-1y substituted with chlorine, bromine, trifluoromethyl or N0 R and R canbe the same or different and either one is selected from the groupconsisting of hydrogen, C -C alkyl, C -C chloroalkyl, phenyl optionallysubstituted with chlorine or nitro and C -C alkoxy'. X is one selectedfrom the group consisting of chlorine, bromine, fluorine and a moietydefined by wherein Y can be either 0 or S and R and R can be the same ordifierent and selected from the group consisting of C -C alkoxy, C -Calkyl, C -C alkylthio, phenyl optionally substituted with chlorine orbromine, phenoxy optionally substituted with chlorine or bromine; R andR, can be the same or different and can be selected from the groupconsisting of hydrogen, and C -C alkyl.

Organic compounds represented by this structure have been found to havepesticidal, particularly insecticidal, activity.

Compounds represented by the following structure:

have been found to possess post-emergence herbicidal activity. -In thisstructure, R R R R and R are defined as hereinabove, and Q is oneselected from the group consisting of chlorine, bromine and fluorine.

This is a division of application Ser. No. 31,405 filed on Apr. 23,1970, now abandoned.

This invention relates to novel derivaties of hydantoins. In one aspect,this invention relates to the l-acylphosphoryl derivative of hydantoinsand their use as an insecticide. In another aspect, this inventionrelates to the 3,780,056 Patented Dec. 18, 1973 l-haIoacyl-hydantoinderivatives and their use as post emergence herbicides.

Acyl hydantoin derivatives of this invention are characterized by thefollowing structural formula:

Br- -Ra wherein R is one selected from the group consisting of C -Clower alkyl, optionally substituted by chlorine, bromine, C -C or C -Calkylthio; C -C alkenyl; C3- C alkynyl; C -C cycloalkyl or phenyloptionally sub stituted with chlorine, trifluoromethyl, bromine or N0 Rand R can be the same or difierent and either one is selected from thegroup consisting of hydrogen, C -C alkyl, C -C chloroalkyl, phenyloptionally substituted by chlorine or nitro and C -C alkoxy. X is oneselected from the group consisting of chlorine, bromine, fluorine and agroup defined by wherein Y can be either 0 or S and R, and R can be thesame or different and selected from the group consisting of C -C alkoxy,C -C alkyl, C -C alkylthio, phenyl optionally substituted with chlorineor bromine, phenoxy, optionally substituted with chlorine or bromine,and R and R, can be the same or different and can be selected from thegroup consisting of hydrogen, and C -C alkyl.

The acyl hydantoin derivatives corresponding to the following structure:

Q wherein R R R R and R are as defined hereinabove and Q is eitherchlorine, bromine. or fluorine have been found to be eflectiveherbicides.

Specific examples of compounds having the above compound structure arelisted hereinbelow.

The foregoing compounds can be readily prepared by the following method;

wherein R R R R R and X are the same as defined herein'before and Y iseither Cl or O o onzq The substituted hydantoins (Reactant A) can beprepared according to the methods described in Chemical Reviews, vol.45, June 1950, pp. 403-407.

This reaction can be carried out at temperatures ranging from 25175 C.,preferably 25130 C., under pres sures ranging from 1 to 10 atmospheres,preferably atmospheric pressures, in the presence of a solvent selectedfrom the group consisting of benzene, toluene, xylene dimethylformamide,dimethylsulfoxide at a mole ratio of A/B ranging from 1:1 to 1:20,preferably 1:2. The preferred solvent is toluene.

Reactant C The. compounds of this invention have general pesticidalproperties. They are useful as insecticides and, as

M is either K, Na... NHrand Y, n, and R, are as destated hereinabove,the halogen derivatives have been found to have post-emergenceherbicidal and insecticidal activity.

The compounds of the invention have general herbicidal and insecticidalproperties. They are especially useful in certain types of weed controlsuch as, for example, in application to crop lands to give control ofthe common weeds, without harming the crop plants;-and for the controlof crabgrass in lawns.

Herbicidal and insecticidal compositions of. theinvention are preparedby admixing one or more of the active ingredients defined heretofore, inherbicidally and insecticidally effective amounts with a conditioningagent of the kind used and referred to in the art as a pest controladjuvant or modifier to provide formulations adapted for ready andefficient application to soil or Weeds (i.e., unwanted plants) or foroveralI pesticidal application using conventional applicator equipment.

Thus, the herbicidal and insecticidal compositions or formulations areprepared in the form of solids or liquids. Solid compositions arepreferably in the form of granulars or dusts.

The compositions can be compounded to give homogeneous free-flowingdusts by admixing the active compound or compounds with finely dividedsolids preferably talc, natural clays, pyrophyllite, diatomaceous earth,or flours such as walnut shell, wheat, redwood, soya bean, andcottonseed flours. Other inert solid conditioning agents or carriers ofthe kind conventionally employed in preparing pest control compositionsin powdered form can be used.

Granulars can be compounded by absorbing the compound in liquid formonto a preformed granular diluent. Such diluents as natural clays,pyrophyllite, diatomaceous earth, flours such as walnut shell, as wellas granular sand can be employed.

'In addition, granulars can also be compounded by admixing the activeingredient with one of the powdered diluents described hereinabove,followed by the step of either pelleting or extruding the mixture.

Liquid compositions of the invention are prepared in the usual way byadmixing one or more of the active ingredients with a suitable liquiddiluent medium. In the cases where the compounds are liquids, they maybe sprayed in ultra low volume as such. With certain solvents, such asalkylated naphthalene or other aromatic petroleum solvents, dirnethylformamide, cycloketone, relatively high up to about 50% by weight ormore concentration of the active ingredient can be obtained in solution.v

The herbicidal and insecticidal compositions of the invention whether inthe form of dusts or liquids, preferably also include a surface-activeagent sometimes referred to in the art as a wetting, dispersing, oremulsifying agent. These agents, which will be referred to hereinaftermore simply as surface-active dispersing agents, cause the compositionsto be easily dispersed in water to give aqueous sprays which, for themost part, constitute a desirable composition for application.

The surface-active dispersing agents employed can. be of the anionic,cationic, or nonionic type and include, for example, sodium andpotassium oleate, the amine salts of oleic acid, such as morpholineanddimethylamine oleates, the sulfonated animal and vegetable oils, suchas sulfonated fish and castor oils, sulfonated petroleum oils,sulfonatecl acyclic hydrocarbons, sodium salt of lignin sulfonic acid(goulac),alkylnaphthalene sodium sulfonate, sodium :salts of sulfonatedcondensation products of naphthalene and formaldehyde, sodium laurylsulfate, disodium monolauryl phosphate, sorbitol laurate,pentaerythritol monostearate, glycerol monostearate, diglycol oleate,polyethylene oxides, ethylene oxide condensation products with stearylalcohol and alkylphenol, polyvinyl alcohols, salts, such as the acetateof polyamines from reductive amination of ethylene/carbon monoxidepolymers, laurylamine hydrochloride, laurylpyridinium bromide, stearyltrimethylammonium bromide, cetyldimethylbenzylammonium chloride,lauryldimethylamine oxide, and the like. Generally, the surface-activeagent will not comprise more than about to 15% by weight of thecomposition, and in certain compositions the percentage will be 1% orless. Usually, the minimum lower concentration will be 0.1%.

The herbicidal and insecticidal compositions are applied either as aspray, granular or a dust to the locus or area to be protected fromundesirable plant growth, commonly called 'weeds, i.e. plants growingwhere they are not wanted. Such application can be made directly uponthe locus or area and the weeds thereon during the period of weedinfestation in order to destroy the weeds, but preferably, theapplication is made in advance of an anticipated weed infestation toprevent such infestation. Thus, the compositions can be applied asaqueous foliar sprays but can also be applied as sprays directly to thesurface of the soil. Alternatively, the dry powdered compositions can bedusted directly on the plants or on the soil.

In applying the herbicidal and insecticidal compositions of theinvention for selective weed control as in the control of weeds incotton or corn fields, the compositions are preferably applied afterplanting of the crop seeds but before emergence of the seedlings. Inother words, the applications are of the pre+emergence type.

The active compound is, of course, applied in an amount sufficient toexert the desired herbicidal action. The amount of the active compoundpresent in the compositions as actually applied for destroying orpreventing weeds will vary with the manner of application, theparticular weeds'for which control is sought, the purpose for which theapplication is being made, and like variables." In general/theherbicidal and insecticidal compositions as applied in the form of aspray, dust or granular, will contain from about 0.1% to 100% by weightof theactive compound.

Fertilizer materials, otherherbicidal agents, and other pest controlagents such as insecticides and fungicides can be included in theherbicidal and insecticidal compositions of the invention if desired. 1

The term carrier or diluent as used herein means a material, which canbe inorganic or organic and synthetic or of natural origin, with whichthe active ingredient is mixed orformulated to facilitate its storage,transport, and handling and application to the plants to be treated. Thecarrier is preferably biologically and chemically inert and, as used,can be a solid or fluid. When solid carriers are used, they arepreferably particulate, granular, or pelleted; however, other shapes andsizes of solid carrier can be employed as well. Such preferable solidcarriers can be natural occurring minerals-although subsequentlysubjected to grinding, sieving, purification, and/ or othertreatments-including, for example, gypsum; tripolite; diatomaceousearth; mineral silicates such as mica, vermiculite, talc, andpyrophyllite; clays of the montmorillonite, kaolinite, or attapulgitegroups; calcium or magnesium limes, or calcite and dolomite; etc.Carriers produced synthetically, as for example, synthetic hydratedsilica oxides and synthetic calcium silicates can also be used, and manyproprietary products of this type are available commercially. Thecarrier can also be an elemental substance such as sulfur or carbon,preferably an activated carbon. If the carrier possesses intrinsiccatalytic activity such that it would decompose the active ingredient,it is advantageous to incorporate a stabilizing agent, as for example,polyglycols such as diethylene glycol, to neutralize this activity andthereby prevent possible decomposition of the derivatives of the presentnitrated aryl compounds.

6 For some purposes, a resinous orwaxy carrier can be used, preferablyone which is solvent soluble or thermoplastic, including fusiblematerials. Examples of such carriers are natural or synthetic resinssuch as a coumarone resin, rosin, copal, shellac, dammar, polyvinylchloride, styrene polymers and copolymers, a solid grade ofpolychlorophenol such as is available under the registered trademarkAroclor, a bitumen, an asphaltite, a wax for example, beeswax or amineral wax such as paraffin Wax or montan wax, or a chlorinated mineralwax, or a microcrystalline wax such as those available under theregistered trademark Mikrovan Wax. Compositions comprising such resinousor waxy'carriers are preferably in granular or pelleted form.

Fluid carriers can be liquids, as for example, water, or an organicfluid, including a liquefied normally vaporous or gaseous material, or avaporous or gaseous material, and can be solvevnts or nonsolvents forthe active material. For example, the horticultural petroleum spray oilsboiling in the range of from about 275 to about 575 F., or boiling inthe range of about 575 to about 1,000 F. and having an unsulfonatableresidue of at least about 75% and preferably of at least about 90%, ormixtures of these two types of oil, are particularly suitable liquidcarriers.

The carrier can be mixed or formulated with the active material duringits manufacture or at any stage subsequently. The carrier can be mixedor formulated with the active material in any proportion depending onthe nature of the carier. One or more carriers, moreover, can be used incombination.

The compositions of this invention can be concentrates, suitable forstorage or transport and containing, for example, from about 5 to about90% by weight of the active ingredient, preferably from about 20 toabout wt. percent. These concentrates can be diluted with the same ordifferent carrier to a concentration suitable for application. Thecompositions of this invention may also be dilute compositions suitablefor application. In general, concentrations of about 0.1 to about 10% byweight, of active material based on the total weight of the compositionare satisfactory, although lower and higher concentrations can beapplied if necessary.

The compositions of this invention can also be formulated as dusts.These comprise an intimate admixture of the active ingredient and afinely powdered solid carrier such as aforedescribed. The powderedcarriers can be oiltreated to improve adhesion to the surface to whichthey are applied. These dusts can be concentrates, in which case ahighly sorptive carrier is preferably used. These require dilution withthe same or a different finely powdered carrier, which can be of lowersorptive capacity, to a concentration suitable for application.

The compositions of the invention can be formulated as wettable powderscomprising a major proportion of the active ingredient mixed with adispersing, i.e. deflocculating or suspending agent, and if desired, afinely divided solid carrier and/or a wetting agent. The activeingredient can be in particulate form or adsorbed on thecarrier andpreferably constitutes at least about 10%, more preferably at leastabout 25%, by weight of the composition. The concentration of thedispersing agent should in general be between about 0.5 and about 5%,

by weight of the total composition, although larger or smaller amountscan be used if desired.

The dispersing agent used in the composition of this invention can beany substance having definite dispersing, i.e., deflocculating orsuspending, properties as distinct from wetting properties, althoughthese substances can also possess wetting properties as well.

The dispersant or dispersing agent used can be protective colloids suchas gelatin, glue, casein, gums, or a synthetic polymeric material suchas polyvinyl alcohol and methyl cellulose. Preferably, however, thedispersants or dispersing agents used are sodium or calcium salts ofhigh molecular weight sulfonic acids, as for example, the sodium orcalcium salts of lignin sulfonic acids derived from sulfite cellulosewaste liquors. The calcium or sodium salts of condensed aryl sulfonicacid, for example, the products known as Tamol 731, are also suitable.

The wetting agents used can be noniom'c type surfactants, as forexample, the condensation products of fatty acids containing at least12, preferably 16 to 20, carbon atoms in the molecule, or abietic acidor naphthenic acid obtained in the refining of petroleum lubricating oilfractions with alkylene oxides such as ethylene oxide or propyleneoxide, or with both ethylene oxide and propylene oxide, as for example,the condensation product of oleic acid and ethylene oxide containingabout 6 to 15 ethylene oxide units in the molecule. Other nonionicwetting agents like polyalkylene oxide polymers, commercially known asPluronics can be used. Partial esters of the above acids with polyhydricalcohols such as glycerol, polyglycerol, sorbitol, or mannitol can alsobe used.

Suitable anionic wetting agents include the alkali metal salts,preferably sodium salts, of sulfuric acid esters or sulfonic acidscontaining at least 10 carbon atoms in a molecule, for example, thesodium secondary alkyl sulfates, dialkyl sodium sulfonsuccinateavailable under the registered trademark Teepol, sodium salts ofsulfonated castor oil, sodium dodecyl benzene sulfonate.

Granulated or pelleted compositions comprising a suitable carrier havingthe active ingredient incorporated therein are also included in thisinvention. These can be prepared by impregnating a granular carrier witha solution of the inert ingredient or by granulating a mixture of afinely divided solid carrier and the active ingredient. The carrier usedcan consist of or contain a fertilizer or fertilizer mixture, as forexample, a superphosphate.

The compositions of this invention can also be formulated as solutionsof the active ingredient in an organic solvent or mixture of solvents,such as for example, alcohols; ketones, especially acetone; ethers;hydrocarbons; etc.

Where the toxicant itself is a liquid these materials can be sprayed oncrops or insects without further dilution.

Petroleum hydrocarbon fractions used as solvents should preferably havea flash point above 73 R, an example of this being a refined aromaticextract of kero-f sene. Auxiliary solvents such as alcohols, ketones,and polyalkylene glycol ethers and esters can be used in conjunctionwith these petroleum solvents.

Compositions of the present invention can also be formulated asemulsifiable concentrates which are concentrated solutions or dispersionof the active ingredient in an organic liquid, preferably awater-insoluble organic liquid, containing an added emulsifying agent.These concentrates can also contain a proportion of water, for example,up to about 50% by volume, based on the total composition, to facilitatesubsequent dilution with water. Suitable organic liquids include, e.g.,the above petroleum hydrocarbon fractions previously described.

The emulsifying agent can be of the type producing water-in-oil typeemulsions which are suitable for application by low volume spraying, oran emulsifier of the type producing oil-in-water emulsions can be used,producing concentrates which can be diluted with relatively largevolumes of water for application by high volume spraying or relativelysmall volumes of water for low volume spraying. In such emulsions, theactive ingredient is preferably in a nonaqueous phase.

The present invention is further illustrated in greater detail by thefollowing examples, but it is to be understood that the presentinvention in its broadest aspects, is not necessarily limited in termsof the reactants, or specific temperatures, residence times, separationtechniques and other process conditions, etc.; or dosage level, exposuretimes, test plants used, etc. by which the compounds and/or compositionsdescribed and claimed are prepared and/or used.

EXAMPLE 1 Preparation of 3-chloroacetyl-l-methylhydantoin A mixture of46 g. (10.4 M) of l-methylhydantoin, 88 g. (0.8 M) chloroacetylchloride, and 200 ml. of toluene were refluxed for 6 hrs. The volatileswere removed under reduced pressure leaving the crude product as a browncrystalline solid, wt. 68.6 g.

A sample was recrystallized from ether/methylene chloride for elementalanalyses, M.P. 7273.

Found (percent): C, 38.14; H, 3.84; N, 14.77. Calculated (percent): C,37.80; H, 3.70; N, 14.70.

EXAMPLE 2 Preparation of 1-t-butyl-3-chloroacetyl hydantoin A mixture of40.0 g. (0.26 M) of l-t-butyl hydantoin, 66 g. (0.6 M) ofchloroacetylchloride, and 250 ml. of toluene were refluxed for 4 hours.The clear brown reaction solution was then stripped, leaving 49 g. ofbrown crystalline solid.

An analytical sample was prepared by recrystallization from ether, M.P.103-1045.

Analysis.Found (percent): C, 46.41; H, 5.60; N, 11.96. Calculated(percent): C, 48.53; H, 5.88; N, 12.50.

EXAMPLE 3 Preparation of 1-allyl-3-chloroacetyl hydantoin A mixture of70 g. (0.5 M) of l-allyl hydantoin, 100 g. of chloroacetyl chloride, and250 ml. of toluene were refluxed for 4 hours. The cool, pale yellowreaction solution contained a precipitate which was filtered, wt. 30.0g., M.P. 84-6". The remaining product was obtained by removing thevolatiles under reduced pressure from the filtrate. This gave anadditional 70.0 g. of product.

The structure was confirmed by NMR analysis.

EXAMPLE 4 Preparation of 3-chloroacetyl-1-(fl-methoxyethyl) hydantoin Amixture of g. (0.5 M) of l-p-methoxyethyl hydantoin and g. ofchloroacetyl chloride were refluxed in 250 ml. of toluene for 4 hours.From the clear brown reaction solution, volatiles were removed underreduced pressure to give 115.4 g. of brown crystalline solid.

The solid was shown to be about 75% pure product by NMR analysis.

EXAMPLE 5 Preparation of S-[1-methylhydantoinyl-3-acyl] phosphorothioateGEN O=L J=O N 1:0 0 $1133 1%(0 01115):

A mixture of 19.0 g. (0.1 M) of 1-methyl-3-chloroacetyl hydantoin, 19.0g. (0.1 M) of S-ammonium-0,0'-diethoxy phosphorothioate, and ml. ofacetonitrile was refluxed for 1.5 hrs. The reaction mixture wasfiltered, stripped on a rotary evaporator (15 mm. Hg/ 40), and theresidue dissolved in 150 m1. of chloroform. The chloroform solution waswashed with 50 ml. cold water twice, twice with 50 ml. of 5% aqueousbicarbonate solution, and dried over anhydrous sodium sulfate. Thechloroform solution was filtered and the volatiles removed on a rotaryevaporator at 15 mm./50'and then under high vacuum (0.1 mm.) at 50 for48 hrs.

EXAMPLE 6 Preparation of 'S 1methyl-3-hydantoinylacetyl) -0,0'- diethoxyphosphorodithioate on,N

.10 EXAMPLE 7 v v A number of phosphoric and thiophosphoric acid esters.oil-substituted hydantoins and 3.-substituted hydantoins were preparedaccording to the procedures previously outlined in Examples 1 and 2. Thecompounds-prepared are listed in Table I. I

The present invention is further illustrated in greater detail by thefollowing examples, but it is to be understood that the presentinvention, in its broadest aspects, is not necessarily limited in termsof the reactants, or specific temperatures, residence times, separationtechniques and other process conditions, etc.; or dosage level, exposuretimes, test plants used, etc., by which the compounds and! orcompositions described and claimed are prepared and/ or used.

TABLE L-HYDANTOINYL PHOSPHOROUS ESTERB A mixture of 10 g. (0.05 M) of3-chloroacetyl-1-methyl hydantoin, 10 g. (0.05 M)S-ammonium-0,0'-diethoxy phosphorodithioate, and 100 ml. of acetonitrilewere recool to room temperature, filtered, stripped on a rotaryevaporator 15 mm. Hg), and then dissolved in 150 ml. chloroform. Thechloroform solution was washed with 50 m1. 5% aqueous bicarbonate, '50ml. of saturated NaCl solution, and then dried over sodium sulfate(anhydrous). The chloroform solution was filtered and the volatilesremoved on a roary evaporator first at 15 mm. Hg/50 and then for 18 hrs.at 50/0.l mm. Hg. The residue was a clear pale brown oil, wt. 14.4 g.

The structure of the product was confirmed by NMR and elementalanalysis.

Elemental analysis.-Calculated (percent): C, 35.29; H, 5.03; N, 8.23.Found (percent): C, 35.42; H, 5.17; N, 8.08.

.fluxed -for Z hrs. The reaction mixture was ...al10.wed..to.

EXAMPLE 8 Representative derivatives of the haloacylated hydantoincompounds of this invention were evaluated for postemergenceactivity.-The test procedure was as follows:

Two flats containing six weeds whose first true leaves have appearedwere sprayed at a rate of 10 lb./a. The flats werethen held in thegreenhouse and the response rated after 12-16 days. Response is rated ona 1-10 scale where 1'=no injury and 10=complete HERBICIDAL TESTING orl-mn'rnYL-a-onnononen'rrn V HYDANTOIN [Post emergence] Weeds Mo CG-BG Fxzrlvru Concentration, 10lb./a 7 10 9 10 9 10 Mexican bean beetle Beanleaves were dipped in the emulsion ofthe test chemical and allowed todry. The individually treated leaves were placed in Petri dishes andfive Mexican bean beetle larvae introduced into each of the tworeplicate dishes.

Mite contact Potted bean plants infested with the two spottedspidermites were placed on a turntable and sprayed with a forofithete'st cheinical. The plants wereheld for two'days iiand the degree of:aphid control was rated; 1 i

1 Aphid systemic v a Nasturtium plants are treated by applying 20milliliters of the formulated test chemical to the soil. The mitesweretransferred to the plant after-I 24 hours. The plants were held .for 48additionalhourstand the degree of the aphid control rated. vv I, v

Boll weevil Five mixed sex adult boll'weevils placed in a wire screencage were sprayed with the proper concentration of formulated testchemical. The boll weevils were provided with succrose solution on afilter paper. The cages were held at about F: for 24 hours and thepresent mortality read after 24 hours.

The compounds were also tested against Southern Army Worm (classLepidoptera), other insects of aphid (order- Homoplera), other membersof the coleopterous order,

. such as confused flour beetle and spider beetle, and against resistantmites and were found to be active. The results of the insecticidalevaluations are given in Table II.

TABLE II.-INSECTICIDAL ACTIVITY OF HYDAN'IOIN-Zi-AND -1-ACYL PHOSPHORICACID ESTER DERIVATIVES to N Mortality (percent) at 250 p.p.m.

I Aphidcontact Potted nasturtium plants infested with the bean aphidswere placed on a turntable a melted with a formulation Mites b ContactSystemic Bean aphids c om Compound M133 1 Adults Nymphs Adults NymphsContact Systemic rootworm R1=C0CH2SP(O CaHr)! 100 90 80 so 0 RI=CH| IR1=COCHSP(O 0B,), 100 100 90 100 100 90 90 so R =CH Rz=o0cH,sP oC,H;)z 0100 90 100 100 o 20 0 R =CH S (DCIH7) 0 o o 0 0 0 0 0 R&COCH1SP OCQH;

R =COCH2SP(0C2Ha)| 60 m=on cnm v R=C0CH:8P(OC3H5): I 100 0 o u o a o, 0so RZ=CH(CH;): p l

v I MIBB=,Mexican bean beetle.

Mites=2 spotted spider mites. v ComRootworm run at 2.5 p.p.m. mulationof the test chemical. The plantswere held for What is claimed is: -7days andthe degree of mite control was rated after this 1. A compound ofthe formula period. I 65 V i RN-CH Mites'systemic 1 I I Bean plants weretreated by applying 20 milliliters of 0= =0 t-hedormul-atedtest-chemical tothe--so1l-.-The-m1tes were J v I transferred .totheplantslafter 24 hours. The plants were 70 =0 held for Zmore days and thedegree of mite control rated. (iHr-s-J-R,

wherein R is alkyl of from 1 to 6 carbon atoms; R alkylthio of from 1 to6 carbon atoms; R is alkoxy of from 1 to 6 carbon atoms; and Y is oxygenor sulfur.

2. A compound according to claim 1 which is S-[(1-methylhydantoinyl)-3-carbonylmethyl]-0,0-diethyl phosphorothioate.

3. A compound according to claim 1 which is S-[(1-methylhydantoinyl)-3-carbonylmethyl]-0,0-diethyl phosphorodithioate.

4. A compound according to claim 1 which is S-[(1- methylhydantoinyl) 3carbonylmethyl]-O-ethyl-S-npropyl phosphorodithioate.

5. A compound according to claim 1 which is S-[(1- methylhydantoinyl) 3carbonylmcthyl]'0,0-dimethyl phosphorothioatc.

6. A compound according to claim 1 which is S-[(1- methylhydantoinyl) 3carbonylmethyl]-0,0-dimethyl phosphorodithioate.

' 14 References Cited UNITED STATES PATENTS 2,928,841 3/1960 McConnellct a1. 260-3095 3,406,179 10/1968 Jamison 260-309.7 5 FOREiGN PATENTS 16,900,039 7/1969 Netherlands 260-30 9.5

1,450,599 7/1966 France 260-2474 10 1,146,486 4/1963 Germany 260--247.1

NATALIE TROUSOF, Primary Examiner us. c1. X.R.

